1. Field of the Invention
Liquid confections having different colors and flavors (all substantially transparent) have been sold for subsequent freezing to an icy consistency ("ice pops"). These liquid confections are generally packaged in plastic packs, such as those made of polyethylene, cellophane and other similar films. Such confections comprise suitable flavoring, sugars, such as cane and corn sugars, acid, vegetable gum stabilizer and preservative, such as sodium benzoate and potassium sorbate or sorbic acid. The confection is conventionally sealed in the plastic film and is ordinarily sold in liquid form at room temperature. The thus-packaged confection is designed to be frozen prior to eating. A recent patent for a non-transparent chocolate-flavored confection of this general type, but requiring xanthan-gum stabilization, is U.S. Pat. No. 3,784,715.
2. Description of the Prior Art
Stabilized liquid or semi-liquid food compositions with or without milk and having a chocolate or other flavor have been prepared over the years. Such compositions are considered by Hunter (U.S. Pat. No. 1,043,839) and North (U.S. Pat. No. 1,710,507). North suggests the use of vegetable gum, such as Irish moss, as a thickener for his milk-containing compositions. Schweigart (U.S. Pat. No. 1,887,905) considers the importance of controlling the acidity of food concentrates and indicates the types of acids which are useful for this purpose. Linn (U.S. Pat. Nos. 1,989,758 and 2,014,623) indicates that stabilizing gums for chocolate compositions (with or without milk) include pectins, such as Irish moss. Pectin is used under controlled pH conditions to obtain substantially-uniform stable suspensions and to improve the consistency or "body" of chocolate beverages by Joseph (U.S. Pat. No. 1,993,932). Irish moss is combined with alginate by Green (U.S. Pat. No. 2,097,224) in a chocolate milk drink. A more chewy frozen milk product, such as ice cream, is provided by Green (U.S. Pat. No. 2,097,225) by combining Irish moss and alginate in milk-containing compositions.
Whittingham (U.S. Pat. No. 2,493,732) relates to a chocolate syrup wherein pectins are used as a dispersoid under controlled pH conditions. Carrageenin is used by North (U.S. Pat. No. 2,672,419) in a concentrated milk-containing frozen mix, which is flexible (as distinguished from a stiff-frozen condition) and which, on thawing and on being reconstituted with cold water, produces a chocolate drink. Kohler (U.S. Pat. No. 2,854,340) relates to frozen desserts in which stabilizers are used under controlled acidic conditions; these desserts have a milk base and chocolate or fruit flavor. Smith (U.S. Pat. No. 3,385,714) uses a combination of carrageenin and sodium carboxymethylcellulose as a viscosity-controlling agent in his liquid milkshake mixes, which contain non-fat milk solids (NFMS). Hotelling (U.S. Pat. No. 3,486,905) finds carrageenan, when used alone, as an inadequate stabilizer in chocolate beverage compositions containing NFMS. In enumerating stabilizers for NFMS-containing food compositions (including ice cream mixes, pie fillings and puddings), Steward (U.S. Pat. No. 3,666,497) lists carrageenin and pectins separately, as well as sodium carboxymethylcellulose.
Definitions
Several terms used in the prior art and used in describing the present invention have meanings which are not always ultimately clear. Since prior art indicates that Irish moss is illustrative of what is meant by "pectins", the relationship between "pectins", "LMP" and "CGN" is provided by these definitions. References in the prior art to pectin or to pectins are not references to LMP unless such is specifically indicated. There is a significant difference between pectin and LMP, and background authority for this significant difference is provided in the following definitions:
brix scale
a hydrometer scale for aqueous sugar solutions so graduated that its readings in degrees Brix at a specified temperature represent percentages by weight of sugar (sucrose) in the solutions ("Webster's Third New International Dictionary", page 279, G. & C. Merriam Company, Springfield, Mass, 1971); in the food industry it is also a measure of percent total soluble solids. Since most solids in the subject products are water soluble, Brix provides a good measure of the weight of the solids expressed as a percent of the total weight.
carboxymethylcellulose
(CMC) a thickening, suspending and stabilizing agent ("The Encyclopedia of Chemistry", second edition, page 195, Van Nostrand Reinhold Company, 1966).
carrageen, carragheen
Irish moss ("Hackh's Chemical Dictionary" fourth edition, page 136, McGraw-Hill Book Company, 1969)
carrageenan
(CGN) a naturally-occurring hydrocolloid consisting of high-molecular weight linear sulfated polysaccharides. It is obtained commercially by extraction from several related species of red algae seaweed and is widely used in the food industry as a stabilizer and gelling agent ("CARRAGEENAN", a Scientific Status Summary of the IFT Expert Panel, Institute of Food Technologists, 1973); -- an extact of various Floridea algae (Rhodophycea) belonging to the genera, Gelidium, Chondrus, Polyides and Gigartina; the most known carrageenans are lambda-, kappa-, iota-, mu- and nu-carrageenans, which are, in particular, described by Janistyn, H., and Huethig, Alfred, "Handbuch der Kosmetika und Riechstoffe", pages 181 and 182, Verlag Heidelberg, 1969; the average molecular weight of carrageenans is between 100,000 and 1,000,000.
carrageenin
highly depolymerized derivative of carrageenan (U.S. Pat. No. 4,029,760);
a water-soluble extractive from carragheen; used as a stabilizer, for suspending cocoa in chocolate manufacture and to clarify beverages ("Hackh's Chemical Dictionary", supra).
cocoa
either natural-process cocoa, bittersweet chocolate or chocolate liquor having equivalent cocoa solids content; wherever the term "cocoa" is used in this specification or the claims, it will be understood to include chocolate material having the equivalent in cocoa solids, as well as cocoa per se. Cocoas generally contain from about 8 to 28 weight-percent fat. While low-fat cocoas having about 8 to 14, and preferably 10 to 12, weight-percent fat are preferred, higher-fat cocoas, such as those having from 16 to 22 weight percent may also be used. The cocoa should be present in the compositions of the present invention in amounts of about 1 to 5 weight percent. The compositions suitably contain, e.g., a mixture of low fat cocoas, and a particularly preferred chocolate-flavored liquid confection has about 1 to 2 weight percent of natural-process cocoa.
food acid
any acid suitable for use in food, including both organic, e.g. citric, tartaric, malic, fumaric and lactic, acid, and inorganic, e.g. phosphoric, acid.
gel
a large number of micelles separated by exceedingly thin films of liquid dispersion-medium; distinguished from sols by the fact that they possess form and offer resistance to deformation even though their liquid phase may comprise a large proportion; under certain circumstances, some sols "set" completely to a jelly-like mass, called a gel; this process is called gelatinizing, gelatinization or gelation (MacDougall, "Physical Chemistry", revised edition, pages 665 and 705, The Macmillan Company, 1943)
a colloid in a more solid form than a sol; a semisolid apparently homogeneous substance that may be elastic and jelly-like (as gelatin) or more or less rigid (as silica gel) and that is formed by coagulation of a sol in various ways (as by cooling, by evaporation, or by precipitation with an electrolyte); a disperse system consisting typically of a high-molecular weight compound or an aggregate of small particles in very close association with a liquid ("Webster's Third New International Dictionary", supra, page 243)
jelly
a semitransparent easily-melted food preparation having a soft somewhat elastic consistency due to the presence of gelatin, pectin, or a similar substance; a fruit product made by boiling sugar and the juice of fruit containing pectin ("Webster's Third New International Dictionary", supra, page 1213)
In the preparation of fruit jelly, a proper combination of acid, pectin and sugar in water must be attained to form a gel. Acceptable gel formation requires a balance of acid, pectin and sugar concentrations (which are interdependent) with other variables. Only a very weak gel forms at a pH below 2.9, and no gel forms at a pH above 3.5. A jelly is a semi-solid food. It is made from not less than 45 parts by weight of fruit juice for each 55 parts by weight of sugar, the resulting product being concentrated to not less than 65 percent by weight of soluble solids ("McGraw-Hill Encyclopedia of Science and Technology", third edition, volume 5, page 454, McGraw-Hill, Inc., 1971).
pectic acid
any of the pectic substances composed mostly of colloidal polymeric galacturonic acids and essentially free from methyl ester groups.
pectic substance
any of a group of complex colloidal carbohydrate derivatives of plant origin containing a large proportion of units derived from galacturonic acid and subdivided into protopectins, pectins, pectinic acids and pectic acids.
pectin
any of the group of colorless amorphous methylated pectic substances occurring in plant tissues or obtained by restricted treatment of protopectin (as with protopectinase or acids) that are found in or obtained esp. from fruits or succulent vegetables, that yield viscous solutions with water and, when combined with acid and sugar in proper concentration, yield a gel constituting the basis of fruit jellies, and that (on hydrolysis) yield pectic acids and methanol; esp: a pectinic acid containing at least 7 to 8 percent methyl ester groups expressed as methoxyl ("Webster's Third New International Dictionary", supra, pages 1662 and 1663)
pectins or high-ester pectins (HEP) are pectinic acids that contain at least 7 or 8 percent methyl ester (expressed as methoxyl) while the low-ester (low methoxyl) pectins (LMP) contain less than 7 percent (usually 3 to 5 percent) methoxyl; under suitable conditions, pectins will form jellies with sugar and acid, whereas the low-ester pectins will form gels with traces of polyvalent ions; pectins form firm jellies when combined with over 50 percent by weight of sugar and at a pH below 3.6. The manufacture and use of low-ester pectins and low-ester gels are regarded as new, separate, distinct and significant developments in pectin chemistry and technology. Low-ester pectins form gels with traces of calcium at sugar concentrations far below and even in the absence of the customary 65 percent used in jams and jellies; the formed gels often show an undesirable extent of syneresis, probably due to heterogeneity of constituent pectinic acids ("The Encyclopedia of Chemistry", supra, pages 783 and 784).
Commercial designation of pectin as jelly grade refers to the weight of sucrose which one unit weight of pectin (at suitable conditions of acidity) will form into a jelly containing 65 percent of sugar solids. Jelly grades between 150 and 300 reflect good commercial-grade pectins. To gel a high-ester pectin, no extensive cooling is required, whereas low-ester pectins, containing less than 7 percent (usually from 3 to 5 percent) methoxyl, gel only when cooled or when multivalent cations are added in small amounts (even at sugar concentrations far below 65 percent) ("McGraw-Hill Encyclopedia of Science and Technology", supra, volume 9, page 691)
pectins [according to U.S. Pat. No. 1,989,758 (page 1, right column, lines 29 and 30) and U.S. Pat. No. 2,014,623 (page 2, left column, lines 11 and 12)] are exemplified by Irish moss, citrus pectin and apple pectin; all references to pectins are to high-ester or high-methoxyl pectins in the absence of some express indication to the contrary.
pudding-like
the consistency at room temperature of the non-settling compositions of this invention is that of what may be regarded as a loose gel; it is on the verge of being semi-solid and is clearly scoopable.